Certain polyepoxide modified phenolaldehyde resins, their oxyalkylation derivatives,and method of making same



United States Pat CERTAIN POLYEPDXIDE MODIFIED PHENOL- ALDEHYDE RESINS, THEIR OXYALKYLATION gERlVATIVES, AND 'METHOD OF MAKENG Melvin De Groote, St. Louis, and Kwan-Ting Shen, Brentwood, Mo., assignors to Petrolite Corporation, Wilmington, Del., a corporation of Delaware N Drawing. Original application December 8, 1952,

Serial No. 324,814. Divided and 3, 1956, Serial No. 582,349

14 Claims. (Cl. zeo -ssj this application May This application is a division of our co-pending appli cation Serial No. 324,814,'filed December 8, 1952, now abandoned. l

Our invention is concerned with new chemical'products or compounds useful as demulsifying agents in processes or procedures particularly adapted for preventing, breaking or resolving emulsions of the water-in-oil type, and particularly petroleum emulsions. Our invention is also concerned with'the application of such chemical products or compounds in various other arts and industries as well as with methods of manufacturing the new chemical products or compounds which are of outstanding value in demulsification.

v I or for that matter as oxyalkylation-susceptible and imine- 2,828,283 Patented Mar. 25, 1958 that the reaction products of the selected resins herein described and the epoxides are apparently'new per'se and may be utilized in a manner other than specifically described herein, it is obvious they represent part of the instant invention. between the resinousmaterials and the imine type reactant exemplify new compounds having properties usually found in cationic surface-active agents and can be used for the purposes for which these materials are commonly employed. The materials so obtained are still susceptible to oxyalkylation with an alkylene oxide, such as'ethylene oxide, propylene oxide, etc., and can be reacted with, these oxides in the same manner as herein described inconnection with the resinous materials which have not been subjected to the intermediate reaction with an imine.

Actually any reference in the claims or specification to the property of being oxyalkylation' susceptible might just as properly be characterized as being imine-reactive" reactive.

' The products derived by reaction between the resins and the polyepoxides have been characterized as being acylation-susceptible as well as oxyalkylation-susceptible. This is due to the fact that reaction yields, on the average,

2 or more alcoholic hydroxyl groups per molecule. Such aliphatic hydroxyl groups as differentiated from phenolic hydroxyl groups are particularly susceptible to acylation The products of our invention are oxyalkylation deriva-' tives of the reaction products of certain phenolaldehyde resins, hereinafter described in detail with certain phenolic polyepoxides, also hereinafter described in detail. Of

particular importance are the oxyalkylation derivatives of the reaction products of phenol-aldehyderesins derived from difunctional monohydric phenols and aldehydes having not over'8 carbon atoms, particularly, formaldehyde, in which the difunctional monohydric phenol residue is derived from a hydrocarbon substituted phenol with phenolic diepoxides of the following formula:

and cogenerically associated compounds formed in its preparation.

The products previously described, which are obtained by oxyalkylation and which, in turn, are useful for various purposes including the resolution of petroleum.

emulsions of the water-in-oil type, are obtained from certain heat-stable resins, which, since they are heatstable, are also susceptible to reaction in various ways;

to yield products other than oxyalkylation products, such as imine derivatives. Such imine derivatives may be obtained, for example, by subjecting the resins to reaction with ethylene imine, propylene imine, or similar iminc's rather than reaction with ethylene oxide, propylene oxide, etc. Comparable compounds are obtained by derivatives which, in addition to having the imine radical, have an ether linkage such as H H R-O-CwCH wherein R is a comparativelysrnall acylradical, such as methyl, ethyl, propyl, etc. In light of fact, i. e.,

with various carboxylic and noncarboxylic acids. They; may be reacted with detergent-forming monocarboxyacids, particularly higher fatty acids, which are saturated or unsaturated, as Well as polycarboxy acids, such as phthalic anhydride, maleic anhydride, etc. Similarly, they can be reacted with maleic acid or a fractional maleic acid ester; such as the monooctyles'ter of maleic acid, and the neutral ester obtained can be reacted with sodium bisulfite' so as to introduce a sulfonic group.

Thus, another phase'of the present invention relates to such resinous compounds and the method of making same.

Notwithstanding the fact that subsequent data will be presented in considerable detail, yet the descriptionbe comes somewhat involved and certain facts should be kept in mind. The epoxides, and particularly the diepoxides may have no connecting bridge between the phenolic nuclei as in the case of a diphenyl derivative or may have a variety of connecting bridges, i. e., divalent linking radicals. Our preference is that either diphenyl compounds Statedanother way we would prefer to use materials of the kind described, for example in U. S. Patent 2,530,-

353, dated November 14, 1950. Said patent describes compounds having the general formula V V Xe n,o--on-on,-oj R,-

wherein R is an aliphatic hydrocarbon bridge, each n independently has. one of the values 0 and 1, and X is an alkylradical'containing from to 4 carbonat'oms The resultants, obtained by reaction The patents hereinafter referred to as concerned with polyepoxides are included in the list immediately following:

U. S. Patent N o. Dated Inventor 2,122.958 Ju1y5,1938= Schafer.

' December 13, .1938 .Mikcs'ka et a1.

September 26. 1939 Do. April2. 1940 Do. July 16. 1940 Cohen et al. June 3. 1941 Rosen et a].

June l7 1941 Rosen. June 9, l942. Britten et al.

November 4J1947. De Groote et al. December 28, 1948 Swern et al. February 15, 1949 Wyler. .do Do.

September 27, 1949. Dietzlcr. November 15, 1949 Mlkeska et a1. April 4, 1950 L Dietzler. et al. A pril 11.1950 Bock et a1.

Bender et a1. Stevens etal.

- Do. Do. Dietzler vHavens. V

. 'De Groote et al.

Newey et a1. Zech. do Albert.

January 22, 19 Greenlee.

The compounds having two oxirane rings and employed for combination with the phenol-aldehyde resin are compounds of the following formula and cogenerically associated compounds formed in their preparation:

in which R represents a divalent radical including. ketone residues formed by theelimination of the ketonic oxygen atom and aldehyde residues obtained by the elimination of the aldehydic oxygen atom, the divalent radical S?S-V; and R Q is the divalent radical obtained by the elimination of a hydroxyl hydrogen atom anda nuclear hydrogen atom from the phenol IBl III RI! in which R', and R", and R' represent hydrogen and. hydrocarbon substituents of the aromatic nucleus, said substituent member having not over 18 carbonatorns; n represents an integer including zero 'and 1, and n represents a whole number not greater than 3. The above mentioned compounds and those congenerically associated compounds formed in their preparation are thermoplastic and organic solvent soluble. Reference to being thermoplastic characterizes them as being liquids at ordinary temperature or readily convertible to liquids by merely heating below the point of pyrolysis and thus differentiates them from infusible resins. Reference to being soluble in an organic solvent means anyof'the be one which is not susceptible to oxyalkylation, as for.

5 the example of the simplest diepoxide which contains at 4- usual organic solvents, such as alcohols, ketones, esters, ethers, mixed solvents, etc. Reference to solubility is merely to dilferentiate from a reactant which is not soluble and might be not only insoluble but also infusible. Furthermore, solubility is a factor insofar that it is sometimes desirable to dilute the compound containing the epoxy rings before reacting with amine. In such instances, of course, the solvent selected would have to example, kerosene, benzene, toluene, 'dioxane, various ketones, chlorinated solvents, dibutyl ether, dihexyl ether, ethyleneglycol diethylether, diethyleneglycol diethylether, and dimethoxytetraethyleneglycol.

The expression fepoxy is not usually limited to the 1,2-epoxy ring. The l,2-epoxy ring is sometimes referred to as the oxirane ring to distinguish it from other epoxy' rings- Hereinafter the Word epoxy unless in-. dicated otherwise, will be used to mean the oxirane ring, i. e., the 1,2-epoxy ring. Furthermore, where a compound has two or more oxirane rings they will be referred to as polyepoxides. They usually represent,'of course, 1,2-epoxide-rings or oxirane rings in the alphaomega position. This. is a departure, of course, from the standpoint of a strictly formal nomenclature as in *least 4 carbon atoms and is formally described as 1,2

components, of the resultant or reaction product described in the previous text, it may be important to note that somewhat similar compounds, generally of much higher molecularweight, have been described as complex resinous epoxides which are polyether derivatives of. polyhydric phenols containingan average of more than one epoxide group per molecule and free from functional groups other than epoxide and hydroxyl groups. See U. S. Patent No. 2,494,295, dated January 10, 1 950, to Greenlee. The compounds here included are limited to the monomers or the low molal members of such series and generally contain two epoxide rings per molecule and may be entirely free from a hydroxyl group. This is important because the instant invention is directed towards products which are not resins and have certain solubility characteristic'snot inherent in resins. Note, for example, that said U; S. Patent No. 2,494,295 describes products wherein the epoxide derivative can combine with asuIfOnam'ideresin. The. intention in said U. S; Patent 2,494,295, of course, is. to obtain ultimately 'a suitable, resinous producthaving the characteristics of a comparatively insoluble'resin. The intent in the present instance in, a comparable exampl e'would be to use a sulfonamide (not a sulfonamide resin) and obtain a material which.

does'not have. the. characteristics of an ordinary varnish resinorthe li-kgi e., is permanently soluble, and stays soluble generally as a liquid of ordinary viscosity, or as a thick viscous liquid and may be a thermoplastic solid, and additionally even may bewater-soluble.

.To illustrate the products which represent the subject matter of the present invention reference will be made to a reaction involving of the oxyalkylating agent, i. e., the compound having two oxirane rings and a phenol aldehyde resin. 5 Proceeding with the example previously d'escribedit i's'obvious' the reaction ratio of two moles of the resin to one mole of the oxyalkylating agent gives'a product which may be indicated as follows:

venience in referring to the mono-epoxide derivatives only.-

(phenol-aldehyde resin) in which the various characters have their prior significance. However, molal ratios may be varied as noted subsequently.

Such final product in turn also must be soluble but solubility is not limited to an organic solvent but may include water. For instance, the products freed from any solvent can be shaken with five to twenty times their weight of distilled water at ordinary temperature and are at least self-dispersing, and in many instances water-soluble, in fact, colloidally soluble.

Similarly, derivatives can be obtained by use of a product having both a nitrogen group and a l,2-epoxy group, such as 3-dialkylaminoepoxypropane. See U. S. Patent No. 2,520,093, dated August 22, 1950, to Gross.

As far as the use of the herein described products goes for the purpose of resolving petroleum emulsions of the water-in-oil. type, and also for that matter for numerous other purposes where surface-active materials are effective, and particularly for those uses specified elsewhere herein, we prefer to employ oxyalkylated derivatives, which are obtained by the use of mono-epoxides, that is, ethylene oxide, propylene oxide, butylene oxide, glycide or methyl glycide or combinations or mixtures thereof, in such manner that the derivatives so obtained have sufficient hydrophile character to meet at least the test set forth in U. S. Patent No. 2,499,368, dated March 7, 1950, to De Groote et al. In said patent such test for emulsification using a water-insoluble solvent, generally xylene, is described as an index of surface activity.

In the present instance the various oxyalkylated derivatives obtained particularly by use of ethylene oxide, propylene oxide, etc., may not necessarily 'be xylene-soluble although they are xylene-soluble'in'a large number of instances. If such compounds are not xylene-soluble the obvious chemical equivalent, or equivalent chemical test, can be made by simply using some suitable solvent, preferably a water-soluble solvent such as ethylene glycol diethylether, or a low molal alcohol, or a mixture to dissolve the appropriate product being examined and then mix with the equal weight of xylene, followed by addition of water. Such test obviously is the same for the reason that there will be two phases on vigorous shaking and surface activity makes its presence manifest. It is understood the reference in the hereto appended claims as to the use of xylene in the emulsification test includes such obvious variant.

Another peculiarity of the compounds herein described is that they may pass into a comparatively high molecular weight range and be effective for various purposes, not only for the resolution of petroleum emulsions but also for other industrial uses described in de tail elsewhere. This characteristic may be related to the fact that the initial resin molecule, obtained in turn from two resin molecules combined by means of a polyepoxide as described, results in a fairly large molecule. We have found we can obtain compounds effective for purposes where surface-active materials are employed, 1

2% of the total'oxyalkylated molecule. The word oxyalkylated is employed this sense forpurpose of conr per molecule.

(phenol-aldehyde resin 7 the polycpoxide and particularly the diepoxide reactant;.

Part 2 is concerned with certain theoretical aspects of diepoxide preparation;

Part 3, Subdivision A, is concerned with the preparer tion of monomeric diepoxides, including Table I;

- Part 3, Subdivision B, is concerned with the preparation of low molal polymeric epoxides or mixtures containing low molal polymeric epoxides as well as the monomer and includes Table II;

Part 3, Subdivision C, is concerned with miscellaneous phenolic reactants suitable for diepoxide preparation;

Part 4 is concerned with suitable phenol-aldehyde resins to be employed for reaction with the epoxides;

Part5 is concerned with the reactions involving the two preceding types of materials and examples obtained by such reaction. Generally speaking, this involves nothing more than a reaction between 2 moles of a previously prepared phenol-aldehyde resin as described, and one mole of a polyepoxide so as to yield a new and larger resin molecule.

Part 6 is concerned with the oxyalkylation of the previously described resultant or cogeneric mixture which, for sake of simplicity, may be referred to as a polyepoxidederived dimer although such language is merely an approximation of its characteristics. Oxyalkylation refers to use of the previously indicated mono-epoxides.

Part 7 is concerned with the resolution of petroleum emulsions of the water-in-oil type by means of the previously described chemical compounds or reaction products; and

Part 8 is concerned with uses for the products herein described, either as such or after modification, including uses in applications other than those involving resolution of petroleum emulsions of the water-in-oil type.

PART 1 As will be pointed out subsequently, the preparation of polyepoxides may include the formation of a small amount of material having more than two epoxide groups If such compounds are formed they are perfectly suitable except to the extent they may tend to produce ultimate reaction products which are not solventsoluble liquids or low-melting solids. Indeed, they tend to form thermosetting resins or insoluble materials. Thus, the specific objective by and large is to produce diepoxides as free as possible from any monoepoxides and as free as possible from polyepoxides in which there are more than two epoxide groups per molecule. Thus, for practical purposes what is said hereinafter is largely limited to polyepoxides in the form of diepoxides.

As has been pointed out previously one of the reactants employed is a diepoxide reactant. It is generally obtainedv from phenol (hydroxybenzene) or .substituted phenol. 'The ordinary or conventional manufacture or the epoxides usually results in the formation of a cogeneric mixture as explained subsequently. Preparation of the monomer or separation of the monomer from the remaining mass of the co-generic mixture is usually expensive. If monomers were available commercially at the monomer. -Certain monomers have been prepared and described in the literature and will be rcferredto subsequently. However, from a practical standpoint one must weigh the advantage, if any, that the monomer has over other low molal polymers from a cost standpoint; thus we have found that one might as well attempt to prepare a monomer and fully recognize that there may be present,

and probably invariably are present, other low molal polymers in comparatively small amounts. Thus, the materials which are most apt to be used for practical reasons'eare either monomers with some small amounts of polymerspresent or;mixtur es :which havea substantial amount of polymers present. :Indeed, the mixture can be prepared free from monomers and still be satisfactory. Briefly, :then, our preference isto :use the monomer or the monomer with the minimum amount of higher polymers.

:It has been pointed out :previously that, the phenolic nuclei in theepoxide-reactant may be directly united,-or united through ;a variety of divalent radicals; Actually, it is our preference to use those which are commercially available and for most practical purposes it means instances where the phenolic nuclei are either united direct ly withoutany intervening linking'radical, or else united by a ketone residue 01- formaldehyde residue. The commercial bis-phenols available nowin the open market illustrate one class. The diphenyl derivatives illustrate a secondclass, and the materials obtained by reacting substituted monofunctional phenols with an aldehyde illustrate the .third class. .All the various known classes may be used but our preference rests with these classes due to their availability and ease of preparation, and also due to the fact that the cost is lower than in other examples.

Although the diepoxide reactants can be produced in more .than one'way, as pointed out elsewhere, our preference is to produce them by means of the epichlorohydrin reaction referred to in detail subsequently.

One epoxide which can be purchased in the open market and contains only a modest amount of polymers corresponds to the derivative of bis-phenol A. It can be used assuch, or the monomer can beseparated by an added step which involves additional expense. This compound of the following structure is preferred as the epoxide reactant and will be used for illustration repeatedly with :the full understanding that any of the other epoxides described .are equally satisfactory, or that the higher. polymers are satisfactory,.or thatmixtures of the monomer .and :higher polymers are satisfactory. tThe formula for this compound is OH: H H H l TH :H .H w nt -19??? O V CH3 0 Reference has just been made to bis-phenol A and a suitable epoxide derived therefrom. Bis-phenol A is dihydroxy-diphenyl-dimethylmethane, with the 4,4 isomers predominating and with lesser quantities of the 2,2 and 4,2 isomers being present. It is immaterial which one of these isomers is used and the commercially available mixture is entirely satisfactory.

Attention is again directedto the fact that in the instant part, to wit, Part 1, and in succeeding parts, the text is concerned almost entirely with epoxides inwhich there is no bridging radical or the bridgingradicalis derived from an aldehyde or a ketone. it would be immaterial if the, divalent linking radical would be derived from the other groups illustrated for the reason that nothing more than mere substitution of one compound. for the other would be required. Thus, WhBI'lS said hereinafter, although directed to one class or a few classes, applies with equal force and effect to'the other classes of epoxide reactants. V V

If sulfur-containing compounds are prepared they should be .freed from impurities with considerable care for the reason that anytime that a low molal sulfur-concentration.

raining compound can react with epichlorohydrin there may be formed 'a by-product in' which the chlorine happened to be particularly reactive and may represent a product, or a mixture of products, Which-would be unusually toxic, even though in. comparatively small 'con- PART 2 The polyepoxides and particularly'the diepoxides can be derived by more than one method as, for example, the use epi .srohydrinbr glycerol dichloroh-ydrin. if a product such as bis pfhenol A'is employed the ultimate compound in monomeric form employed asa reactant in thepresent invention has the following structure:

' I Y 7 CH3 "n n n n n n w r e r/ 0 on: 'o

Treatment with epichlorohydrin, for example, does not yield this product initially but there is an intermediate produced which can be indicated by the following structure:

Treatment with alkali, of course, forms the epoxy ring. A number of problems are involved in attempting to produce this compound free from 'cogeneric materials of related composition. The difficulty stems from a number ofsources and a few of the more important ones are as follows:

(,1) The closing or" the epoxy ring involves the use of caustic soda or the like which, in turn, is an effective catalyst in causing the ring to open in an oxyalkylation reaction.

Actually, what maythappenvfor any one of a number of reasons is that one obtains a product in which there isonly one epoxide ring'and there may, as a matter of fact, be more than one hydroxyl radical as illustrated by the-following compounds:

(2) Even if one starts with the reactants in the preferred ratio, to wit, two parts of epichlorohydrin to one part of bisphenol A, they do not necessarily so react and as a result one may obtain products in which more than two epichlorohydrin residues become attached to a single bis-phenol A nucleus by virtue of the reactive hydroxyls present which enter into oxyalkylation reactions rather than ring closure reactions.

'(3) .As is well known, ethylene oxide in the presence of alkali, and for. that matter in the complete absence of Water, forms cyclic polymers. indeed, ethylene oxide can produce a solid polymer. This same reaction can, andat times apparently does, take place in connection with compounds having one, or in the present instance, two substituted oxirane rings, i. e., substituted 1,2 epoxy rings. Thus, in many ways it is easier to produce a polymer, particularly a mixture of the monomer, dimer and trimer, than it is to produce the monomer alone.

(4) Ashas been pointed out previously, monoepoxides may be present and, indeed, are almost invariably and inevitably present whenone attempts to produce polyepoxides, and particularly diepoxides. The reason is the" one which has heen indi'cated previously, together with a,828,28s r g 1% the fact that in the ordinary course of reaction a di-' For purpose of brevity, without going any furthen-thsepoxide, such as tzed way, establishes the composition of resinous products OH H H H 8 15 E. H available under the name of Epon Resins as now sold ing 5 the open market. See, also, chemical pamphlet entitled o CHi 0 Epon Surface-Coating Resins, Shell Chemical Corpomay react with a mole of bis-phenol A to give a monoration, New York City. The word Epon is a registered epoxy structure. Indeed, in the subsequent text imtrademark of the Shell Chemical Corporation.

CH8 OH 7 I CH;

'"Oi* -"i CH: CH! l ,(IDHL & O

mediately following refer e nce is made to the dimers, For the purpose of the instant invention, 11' may repretrimers and tetramers in which two epoxide groups are sent a number including zero, and at the most a low numpresent. Needless to say, compounds can be formed ber such as 1,2 or 3. This limitation does not exist in which correspond in every respect except that one termiactual efforts to obtain resins as diflerentiated from the nal epoxide group is absent and in its place is agroup herein described soluble materials. It is quite probable having one chlorine atom and one hydroxyl group, or that in the resinous products as marketed for coating use else two hydroxyl groups, or an unreacted phenolic ring. the value of n is usually substantially higher. Note again (5) Some reference has been made to the presence of what has been sa d previously that any formul at a chlorine atom and although all effort is directed tobest, an over-simplification, or at the most represents perwards the elimination of any chlorine-containing 111198 0n1y the more Important Principal e nt molecule yet it is apparent that this is often an ideal constltuents- These a ls y y f i p e nonapproach rather than a practical possibility. Indeed, the TeSInOIiS to pl s h s ePOXIdeS ich are polyether. same sort of reactants are sometimes employed to obderivatives of p y i Phenols Containing an average tain products in which intentionally there is both an of more than one epOXlde group P molecule a fr epoxide group and a chlorine atom present. See U. S. from functional E P other than ePOXide and y y Patent No. 2,581,464, dated January 8, 1952, to Zech. p

next formula is in essence one which, perhaps in an ideal-.

What has been said in regard to the theoretical aspect Referring nQ Y t What has been n P y, t V i 1 is, of course, closely related to the actual method of prepcompounds having both p t g 0f the eqlllvalent aration which is discussed in greater detail in Part 3', parand a Y Yh O P one need go 110 further than ticularly subdivisions A and B. There can be no clear 40 to consldel' the Thactlon Product Of line between the theoretical aspect and actual preparative 0H,

steps. However, in order to summarize or illustrate what g g g g g has been said in Part 1, immediately preceding reference H H will be made to a typical example which already has been 0 CH3 0 p y P p of iilnstratinn- The Particular and bisphenol A in a mole-for-mole ratio, since the initial 1 ample is reactant would yield a product having an unreacted'epoxy ring and two reactive hydroxyl radicals. Referring again H H H O H H to a previous formula, consider an example where two HC--C-CO OC(/-CH H H moles of bisphenol A have been reacted with 3 moles of 0 0 epichlorohydnn. The simplest compound formed would It is obvious that two moles of such material combine be thus:

OH| ('|)H (3H3 CF11: CH: t (5H; CH: I a at readily with one mole ofbis-phenol A, Such a compound is comparable to other compounds hav- CH ing both the hydroxyl and epoxy ring such as 9,10-epoxy l octadecanol. The ease with which this type of compound H0 0H polymerizes is pointed out by U. S. Patent No. 2,457,329,

CH; dated December 28, 1948, to Swern et a1.

to produce the product which is one step further along, The h diihcuity Which involves teHdeney t0 at least, towards polymerization. In other words, one Pnlytnenze 0n the P Q cntnpounde havlng a reaetlve prior example shows the reaction product obtained from ring and a e Y Tadleal y h Illustrated y 0 1- one mole of the bisphenol A and two moles of epichloro- Pounds Where, Instead Of the exlrane Ting lp y hydrin. :This product in turn would represent three moles ring) there is present a 1,3-epoxy ring. Such compounds of bisphenol A and four moles of epichlorohydrin. are derivatives of trimethylene oxide rather than ethylene fl oxide. See U. .5. Patent Nos. 2,462,047 and 2,642,048, both dated FebruaryJS, 1949,'to Wyler. 1 .At the expense of repetition of what appeared previ ously it may be well to recall that these materials :may

vary from simple soluble non-resinous to complex non 5' or for greater simplicity the formula could be restated thus:

in which the various characters have their prior significance and in which R is the divalent radical obtained from the clas'sof zero and .1, and n' represents a. whole number not greater than 3.

PART vs Subdivision A .The preparations of .the diepoxy derivatives of the diphenols, which are sometimes referred to as diglycidyl ethers, have been described in a number of patents. For convenience, reference'will be made to two only, to wit, aforementioned 'U. S. Patent 2,506,486, and aforementioned U. S. Patent No. 2,530,353.

Purely by way of illustration, the following diepoxides, or diglycidyl ethers as they are sometimes termed, are included for purpose of illustration. Theseparticular compounds are described in the two pat'ents justmentioned.

TABLE I Ex- Patent ample ,Diphenol Diglycidyl ether refernumber ence CH9(C H4OH)-r Di(epoxypropoxyphenyl)methane 2, 506,486 CH3CH(C5H4OH)2 Di(epoxypropoxyphenyl)methylmethane. 2,506,486 (CH3)2C(CsH4OH)2 Di(epoxypropoxyphenyl)dimethylmethane. 2, 506, 486 O2H5C(OH3)(C5H4OH)2 D1(ep0xypropoxyphenyl)ethylmethylmethane 2, 506, 486 (OgHmC B 4 H); Di(epoxypropoxyphenyl)diethylmethane 2, 506,486 CH3C(O3H1) (C6H4OH)2--- 2, 506,486 CH G (C9115) (CQHtOB-DZ. 2, 506, 486 C H C(O H (c6H4OH)2 2, 506, 486 CsH1C (C5115) (05H40H)g 2, 506, 486 C4H O(C5H (C H4OH)2 D (epoxypropoxyphenyl)butylphenylmethane 2, 506, 486 (CH3O H4)CH(CL\H4OH)2v D1(epoxypropoxyphenyl)tolylmethane 2, 506, 486 (01130 114) 0 (CH3) (C HiOEDL Di(epoxypropoxyphenyl) tolylmethylmethan 2, 506, 486 13A Dihydroxy diphenyl 4,4-bis(2,3-ep0xyprcpoxy)diphenyl 2, 530, 353 14A- (0H3) C(C4H .C5H3O H): 2,2-bis(4-(2,3sep0xypropoxy)2-tertiarybutylphenyl) propane- 2, 530, 353

by the elimination of a hydroxyl hydrogen atom and a nuclear hydrogen atom from the phenol in which R, R, and R' represent a member of the class consisting of hydrogen and hydrocarbon substituents of the aromatic nucleus, said substituent member having-not over 18 carbon atoms; n represents an integer selected Subdivision B As to the preparation of low-molal polymeric epoxides or mixtures reference is madeztornurnerous patents and tremely desirable "IOilJCllldGS specific reference to .afore mentionedlU. '8; Patent No. 2,575,558. The reasoniis that this patentincludes the same formula which .has

been referred'toipreviously in :Part.2,'which is'concerned' iii the hereto appended claims.

t, appears in The following examples can be specified by reference bears in mind it is in essence an over-simplification.

. I r TABLE n 0 a H /0\" C- -OC --0Rl[R].R1OC-( C -0 R1[R]..-R1O--CCC H: H H; H H: H: I 7 H: H H! g I a (in which the characters have their previoussigniflcance) Example R1Ofrom H3103 --R 'n 'n' Remarks number B1 Hydroxy benzene CH; 2 1 0,1,2 Phenol known as bis-phenol A. Low

l r polymeric mixture about 3% or more O- where n=0, remainder largely where l 'n'=1, some where n'=2. CH. is. 3 a on. 1 0,1,2 Phenol known-as bis-phenolB. See note a Y regarding B1 above.

Hg Bii...;-l. Orthobutylphenol CH: 1 0,1,2 Even though It is preferably 0, yet the usual react on product might well con- -ctam materials wherevn is 1, or to a j lesser degree 2. v .1 H1

B4........ Orthoamylphenol CH: 1 0,1,2 Do,

Bonus..- Orthooctylphenol CH 1 0,1,2 Do,

no. Orthononylphenol CH 1 0,1,2 Do.

) (EH: B1 Orthododecylphenol on; V 1 0, 1,2 Do. ll l B8 Metacrmm CH, 1 0,1,2 See prior note. This phenol used as initial material is known as bis-phenol -Q-' C. For other suitable bis-phenols see (5 U. 8. Patent 2,564,191. 3* j 39 an (311; 1 0, 1, 2 See prior note.

H, 11H: 1310.....- Dlbutyl (ortho-para) phenol. 1 1 1 0,1,2 p0. v H

311.....- Dlamyl (ortho-para) phenol. g 1 0,1,2 Do.

, K n -B12....-. Dioctyl (ortho-para) phenol- 1g 1 0,1,2 Do.

l H 313.11- Dinonyl(ortho-para)phenol 1g 1 0,1,2 Do.

- 'B14...--. Diamyl (ortho-para) phenolg 1 0, 1, 2 Do.

B15 (in H 1 0,1,2 1 Do. 0 I; I I I CsHr B 10 Hydrcxy benzene l 0. 1, 2 Do.

a a i 1317..-.-. Diamyi phenol (ortho-para). SS l 0,1. 2 Do. M4 an t s 1 0,1,2 Do.

is e 16 TA LE l -woontln e Ems -,alo.i om;.nnioa V +B-; n Remarks number 319..-.-. Dibutylphenol(ortho-para) g 1 0,1,2 See priornote.

nsn (in 15 H 1 0,1,2 Do

7 H H 1321 Dinonylphenol(ortho-para)- lg 1% 1 0,1,2 Do

I n H H 2 flmmxyvh nz 1 S 1 1 p 1 I p v 2 B23 n None 0 0,1,2 Do.

B24 Ortho-tlsoprop ylphenol.,.. CH; 1 0,1,2 See priornote. (AstopreparationoHA'r I isopropylidene bis-(Zisbpropylphenoh V H see U. S. Patent No. 2,482,748, dated g Sept. 27, 1949, to Dietzler.)

Hz fr B25 Para-octyl phenol CH:S CH= 1 0, 1,2 See prior note. (As to preparation of the phenol sulfide see U. S. Patent No.

2,488,134, dated .Nov. 15, 1949, to. I v Mikeska eta1.) e

B26 Hydroxyhenzeue..,. CH; 1 0,1,2 See prior note. (As to preparation or the phenol sulfide see U. S. Patent No.

laHl

Subdivision C wherein R is a substituent selected from the class con- The prior examples have been limited largely to those SIStIPg 0f q 'y butyliand ternary blltyl E PQ and in which there is no divalent linking radical, as in the R 1s a substituent selected from the class consisting of case of diphenyl compounds, or where the linking rad- YL- Y f y 3 a y p alkaIyl p a11d ical is derived from a ketone or aldehyde particularly a Whereln 881d alkyl group contains at least 3 carbon atomsketone. Needless to say, the same procedure is cur- See US Patent ployed in converting diphenyl into a diglycidyl ether IO(CSHO)'H regardless of the nature of the bond between the two phenolic nuclei. For purpose of illustration attention C611.

is directed to numerous other diphenols which can be readily converted to a suitable polyepoxide, and particularly diepoxide, reactant.

As previously pointed out the initial phenol may be p substituted, and the' substituent group in turn may be in which the C H groups are secondary amyl groups. a cyclic group such as thephenyl group or cycloheggyl See U. S. Patent No. 2,504,064. group as in the instance of cyclohexylphenol or phenyl- V 06111; 7 CeHia phenol. Such substituents are usually in the ortho position and may be illustrated by a phenol of the following HO OH composition:

See'IJ. 5. Patent No... 2 28 f5,56 3. OH: H OH: HO 01137 1 11: CH3 7 ,1 7 0H, o0 Similar phenols which are monofunctlonal, for instance, (3H1 paraphenyl phenol or paracyclohexyl phenol with an a a 011-011, additional substituent in the ortho position, may pe V 6 CH:

employed in reactions previously referred to, for Linstance, with formaldehyde or sulfur chlorides to give OHPCH comparable phenolic compounds having 2 :hydroxyls and W V v suitable for subsequent reaction with epichlorohydrin, seeu's'patentNo'2503'196' etc. CH:

Other samples include: r r 7 V V C G 7 OH on, Br J (I) wherein Risamemberof-the group consisting of alkyl, and alkoxy-alkyl radicals containing from 1 to 5 carbon atoms, inclusive, and aryl and chloraryl radicals of the benzene series. See U. S. Patent No. 2,526,545.

wherein R is a substituent selected from the class consisting of secondary butyl and tertiary butyl groups and R is a substituent selected from the class consisting of alkyl, cycloalkyl, aryl, aralkyl, and alkaryl groups. See U. S. Patent No. 2,515,906.

CH=CH on \C=CH on HaC-C-CH:

See U. s. Patent No. 2,515,908.

As to sulfides, the following compound is of interest:

5 11 (EaHu See U. S. Patent No. 2,331,448.

As to descriptions of various suitable phenol sulfides, E reference is made to the following patents: U. S. Patents Nos. 2,246,321, 2,207,719, 2,174,248, 2,139,766, 2,244,021, and 2,195,539.

As to sulfones, see U. S. Patent No. 2,122,958.

As to suitable compounds obtained by the use of formaldehyde or some other aldehyde, particularly compound such as Alkyl Alkyl Alkyl Alkyl in which R and R are alkyl groups, the sum of whose carbon atoms equals 6 to about 20, and R and R, each preferably contain 3 to about 10 carbon atoms, and x is 1 to 4. The term sulfides as used in this text, therefore, includes monosulfide, disulfide, and polysulfides.

PART 4 This part is concerned with the preparation of phenolaldehyde resins of the kind described in detail in U.v S.

and Keiser, with the following qualifications; said aforementioned patent is limited to resins obtained from difunctional phenols having 4 to 12 carbon atoms in the substituent hydrocarbon radical. For the present purpose the substituent may have as many as 18 carbon-atoms, as in the case of resins prepared from tetradecylphenol, substantially para-tetradecylphenol, commercially available. Similarly, resins can be prepared from hexadecylphenol or octadecylphenol. This feature will be referred to subsequently.

In addition to U. S. Patent No. 2,499,370, reference is made also to the following U. S. Patents: Nos. 2,499,365, 2,499,366 and 2.499,367, all dated March 7, 1950, to De Groote and Keiser. These patents, along with the other two previously mentioned patents, described phenolic resins of the kind herein employed as initial materials.

For practical purposes, the resins having 4 to 12 carbon atoms are most satisfactory, with the additional C carbon atom also being very satisfactory. The increased cost of the C and C carbon atom phenol renders these raw materials of less importance, at least at the present time.

Patent 2,499,370 describes in detail methods of preparing resins useful as intermediatesfor preparing the products of the present application, and reference is made tothat patent for such detailed description and to Examples la through 103a of that patent for examples of suitable resins. I

As previously noted, the hydrocarbon substituent in the phenol may have as many as 18 carbon atoms, as illustrated by tetradecylphenol, hexadecylphenol and octadecylphenol', reference in each instance being to the difunctional phenol, such as the orthoor para-substituted phenol or a mixture of the same. Such resins are de- "scribed also in issued patents, for instance, U. S. Patent No. 2,499,365, dated March 7, 1950, to De Groote and Keiser, such as Example 71a.

It is sometimes desirable to present the resins herein employed in an over-simplified form which has appeared from time to time in the literature, and particularly in the patent literature, for instance, it has been stated that the composition is approximated in an idealized form by the formula V 7 OH OH OH H r H1 0 0 OH I H R R n R In the above formula n represents a small whole number sents an aliphatic hydrocarbon substituent, generally an alkyi radical having from 4 to 14 carbon atoms, such as a butyl, amyl, hexyl, decyl or dodecyl radical. Where the divalent bridge radical is shown as being derived from formaldehyde it may, of course, be derived from any other reactive aldehyde having 8 carbon atoms or less.

Inthe above formula the aldehyde employed in the resin manufacture is formaldehyde. Actually some other aldehyde such as acetaldehyde, propionaldehyde, or butyraldehyde may be used. fied thus:

The resin unit can be exempli-f te t l q-2 92370 sat d M rs M DeQmq 1. c

9 inwhich R' -isthe divalent radical. obtainedsfrom the particular aldehyde employed to form the resin.

Aspreviously stated the preparation of resins, the kind herein employed as reactants, is well known. See U; S. Patent No. 2,499,368, dated March 7, 1950, to De Groote and Keiser. Resins can bemade usingranacid'catalyst or basic catalyst or a catalyst showingneither acid nor basic properties in the ordinary sense or without any catalystatall. It ispreterable that the resins employed be substantially neutral. In other words, if prepared by using a strong acid as a catalyst, suchstrong acid should be neutralized. Similarly, if a strong baseis used as a catalyst it is preferable that the base be. neutralized al-. though we have found that sometimesthe, reaction de-. scribed proceeded more rapidly in theprescnceofa small amountof a free base; The ,amount'may be as small as at 200th of a percent and as much as a few 10ths of a percent.; Sometimes moderate increasesin caustic soda' and caustic-potashmaybe used." However, the-mostdesirable.,.procedure. in practically every case is to have the resin neutral... 7

In preparing. resins one doesnot'get a single polymer, i. e., onehavingjust 3 units, or just 4 units, or just 5 units,-.o .just- .6 -un its,- etc'. Itis usually a mixturef for instance, one approximating4 phenolic nuclei will have some trimer and pentamer present. Thus, the molecular reason for using-other than those which are lowest. in.

price and mostreadily. available commercially. For purpose .of convenience suitable resins are characterized in the following table:

TABLEIII M01. wt.

Em Position R of re in ample, R r of R derived n molecule number from-- (ba std on n+2) C1.. Phenyl 3.5 992.5

02. Tertiary butyl 3.5 892.5 03. Secondary butyl... 3.5 882.5 04...... Cyclohexyl. 3.5 1,025.5 C5 Tertiary amylm H 3.5 950.5 C6 Mixed secondary 3.5 805.5

and tertiary amyl. C7 Propyl. 3.5 805.5 08 TertiaryhexyL. 3.5 1, 036.5 C9 Octyl 3.5 1,190.55 010.". NonyL. H. 3.5 1,267.5 C11 Dccyl 3.5 1,344.5 C12 Dodecyl 1.- 3.5 1,498.5 C13... Tertiary butyl. 3.5 945.5

014 Tertiary amy]... 3.5 1,022.5 C 15. Nonyl 3.5 1,330.5 C16 Tertiary butyl 3.5 1,071.5

(317.. Tertiary arnyl 3.5 1. 148.5 C18 Nonyl 3.5 1,456.5 C19... Tertiary butyl 3.5 1, 008.5

dehyde.

020.... Tertiaryamyl.; -do do 3.5 1, 085. C21. ony do do 3.5 1,393. Tertiary butyl 4.2 a 906.

Tertiary amyl 4.2 l, 083,

Nonyl a... 4.2 1,430.

Tertiary hutyl. 4. 8 1, 094.

Tertiary amyl 4.8 1,189.

Nonyl 4.8 1, 570.

Tertiary amy1 1. 5 604.

- CyclohexyL. 1.5 64

Hexyl. 1. 5 653.0

coin-anaemia more" methylate as a catalyst. The amount generally employed PART 5.

As previously stated, the intermediate reactions involve two moles of. a phenol-aldehyde resin of the kind previously described, and one mole of a diglycidyl ether as described. The reaction is essentially an oxyalkylation, but, for sake of convenience is difierentiated from the subsequent oxyalkylation procedure which involves a mono-epoxide only. Since the polyepoxide is nonvolatile as compared, for example, to ethylene oxide, the reaction is comparatively simple.v On the other hand, purely asa matter of convenience,.one generally would'conduct both classes of reactions in the same equipment. In other words, the two moles of phenol-aldehyde resin would bereacted with a polyepoxide and.then subsequently .with a mono-epoxide. In any event,the polyepoxide reaction can be conducted in an ordinary reaction vessel, such as the usual glass laboratory equipment. This is particularly true of the kind used for resin manufacture as described in a number of patents, as for example, U. S. Patent No. 2,499,365. One canuse a variety of catalysts in connection with the polyepoxide of the same class employed with mono-epoxide. In fact, the reaction will go at an extremely slow rate Without-any catalyst at all. The usual catalysts, include alkaline .materials such as caustic soda, caustic, potash, sodium methylate, etc. Other catalysts may be acidic in nature and are of the kind characterized by iron and .tin chlorides. Furthermore,

insoluble catalystsv suchas .clays or specially prepared mineral catalysts have been used. For practical purposes it is best to use a catalyst which can remain in the reaction mass and will continue to serve as a catalyst in. connection with the oxyalkylation employing the monoepoxide. For this reason-we have preferred to use a small amount of finely diyided caustic soda or sodium.

is 1%, 2%; or- 3% of these alkaline catalysts.

Actually, thereactiohs-ofpolyepoxides with various resin materials have been thoroughly described in the'literature and the procedure is, for-all purposes, the sameas with glycide which is described in detail in the next succeeding part, towit, Part 6.

:The -use ofan I. excessive amount of catalyst may produce side reactions as in the case of glycide. For the sake of simplicity the procedure will be illustrated by examples but particulargeferenceis made again to the in an inert solvent, i. e., one that is not oxyalkylationently -an romatic -solvent ,such fas xylene or a higher susceptible. Generally;speaking,,-this is most conveni-,

bQilingcbal tar solyent,,or else a similar high boiling aromatic solvent obtained.from petroleum. Onecan .em-. ploy an oxygenated solvent such as the diethylether of ethylene glycol, or; the. diethylether. of Y propylene glycol, -or similar ethers eithen alone. OrinIcOmbination with a hydrocarbon solyenn, The solvent so, selected should be one which, ot co1 1r se,, is suitable, in the, oxyalkylation step, involving the mono-epoxides described subsequently. The solvent selected-may depend on the ability to remove it by subsequent distillation if required.

Example D1 The phenol-formaldehyde resin employed was the one previously identified as;C38,:having;a molecular weight of approxirnately 700; the amount ,employed was .-1408- grams Th resin was, finely powdered and -1,000 gram s a and stirred, until solutionwas: complete. 25 grarnspf 'ifir drbpwise. Just before the addition of the'diepoxide'solw tion the temperature was raised to 105 C. The time required to add the diepoxide was approximately 1% hours. The temperature rose during this period of time to about 126 C. The product was then allowed to reflux at a temperature of 128 C. for 2 hours. During this period there was a. modest loss of xylene and the temperature rose slightly to 130 C. Heating was then allowed to proceed for another 9 hours and part of the Xylene removed by use of a conventional phase-separating trap, so at the end of the 9-hour. period the temperature was approximately 141 C. Refluxing was then continued further for another 7-hour period, with the removal 'of a small amount of xylene by the use of the phase-separating trap. The temperature at the end of this time reached about 145 C. At the end of this period of time there was a slight residue equivalent to approximately to 14 cc., in the bottom of the reaction flask or pot, and a slight amount of xylene was added-about 100 grarnsin order to have the final reaction mass represent approximately one-half reaction mass and one-half solvent. Subsequent tests in an evaporating dish showed there was approximately 49% reaction mass and 51% solvent.

The procedure employed, of course, is simple in light of what has been said previously and also in light of what is said in the next section. Various examples obtained in substantially the same manner are enumerated and described in the following tables:

7 TABLE VI Probable Probable mol. wt. of Amt. of Amt. or number 01' Ex. No. Resin reaction product, solvent, hydroxyls product grs. grs. per molecule 1. 748 3. 563 1. 815 8 2, 325 4. 650 2. 325 11 2. 105 4. 305 2, 200 11 2. 391 4. 782 2. 391 11 2. 721 '5. 442 2. 721 11 2. 875 5. 750 2. 875 11 2. 231 4. 462 2. 231 11 3. 000 6. 000 3. 000 11 3. 253 6. 506 3. 253 11 2. 357 4. 620 2. 263 11 1. 612 3. 224 1. 612 3 1.836 3. 672 1, 836 8 1. 820 3. 640 1.820 8 l, 550 3. 100 1, 550 7 1. 650 3. 347 1. 697 7 1.650 2.900 1.250 7 1. 720 a. 440 1, 720 I 7 1. 930 3.860 1.930 7 1. 956 3. 012 1. 956 8 2. 533 5, 066 2. 533 11 2. 313 4. 626 2. 313 11 2. 598 5. 302 2. 704 11 2. 928 5. 856 2. 928 11 3. 083 6. 186 3.083 11 2. 438 4. 780 2. 342 -11 3. 208 6.416 3. 208 11 I 3. 461 6. 922 3. 461 11 2. 565 5. 130 2, 565 11 l, 820 3. 714 1. 894 8 2.044 4. 088 2, 044 8 2.028 4. 056 2.028 8 1, 758 3. 516 1, 758 7 1. 848 3. 623 1, 775 7 1.858 3. 334 1,726 7 1, 928 3. 935 2.007 7 2, 138 4. 364 2, 226 "7 At this point it may be desirable to direct attention to two facts, the first being that we are aware that other di- TABLE IV Dissolved Sod. Polyep- Dissolved Approx. Percent.- Resin in math Polyepoxide in Reaction time of age Ex. No. Resin used used. xylene, ylate oxide used, xylene. temp. reaction, solvent grams grams used. used grams grams range, 0. hrs in final grams product 1. 408 1. 000 25 3A '340 500 100-145 18 51 1. 985 1. 000 3A 340 500 90-160 18 1, 765 1. 000 32 3A 340 500 -145 16 61 2. 050 1. 000 36 3A 340 500 80-145 18 50 2. 380 1, 000 41 3A 340 500 80-145 20 50 2, 535 1. 000 43 3A 340 500 90-150 20 50 1, 890 1, 000 33 3A 340 500 90-155 18 50 2. 660 1, 000 45 3A 340 500 80-150 20 50 2. 913 1, 000 49 3A 340 500 90-160 20 50 2, 017 1. 000 38 3A 340 500 90-155 18 49 1, 272 1, 000 24 3A 340 500 90-150 16 50 1. 496 1, 000 28 3A 340 500 90-160 18 50 1. 480 1, 000 27 3A 340 500 90-160 17 50 1, 210 1. 000 25 3A 340 500 -155 18 50 1, 300 1, 000 26 3A 340 500 -150 20 51 1.110 1, 000 23 3A 340 500 -160 18 50 1.380 1,000 28 3A 3-10 500 90-160 22 50 590 1. 000 32 3A 340 500 85-160 22 50 TABLE V Dissolved Sod. Polyep- Dissolved Approx. Percent- Resin in meth- Polyepoxide in Reaction time of age Ex. No. Resin used used, xylene, ylate oxide used, xylene, temp. reaction, solvent grams grams used, used grams grams range, 0. hrs. in final grams product 1, 408 1, 000 28 B1 548 500 -160 18 50 1, 985 1, 000 38 B1 548 500 100-165 18 50 1, 765 1, 000 35 B1 548 500 95-160 18 50 2, 050 1, 000 39 B1 548 500 95-160 20 51 2, 380 1, 000 44 B1 548 500 90-160 20 50 2. 535 1. 000 46 B1 548 500. 90-165 20 50 1. 890 1. 000 36 B1 548 500 90-165 18 49 2, 660 1, 000 48 B1 548 500 90-155 20 50 2, 913 1. 000 52 B1 548 500 100-165 20 50 2, 017 1, 000 40 B1 548 500 100-160 20 50 1, 272 1,000 27 B1 548 500 100-155 16 51 1, 496 1, 000 31 B1 548 500 100-165 18 50 1. 480 1, 000 30 B1 548 500 100-165 18 50 1, 210 1, 000 26 B1 548 500 95-165 20 50 1, 300 1, 000 26 B1 548 500 95-165 20 49 1, 1.000 23 B1 548 500 100-165 21 51 1. 380 1, 000 28 B1 548 500 100-160 23 51 1, 590 1, 000 32 B1 548 500 100-165 19 51 may be employed toreplace the diepoxides-herein described. However, such derivatives are not included as part of the instant invention. g a

At times we .-have found a tendency {or an-insoluble mass to tend toform orgat least {to obtain-incipient crosslinking or gelling CVQlQ-2Whl1 the molal ratjois in the order of 2 moles of resinito oneof diepox idev; WEFhaVB, found this ,can be avoided by anyone otftheffollowing procedures'or' their equivalent. Dilute the resin, orthe diepoxide, orboth, with an inert solvent, 'suchilas xylene or the like. ,In some instances an oxygenated solvent, such as the'diethyl etherof ethyleneglycolmay be employed. Another procedure which is helpful is to reduce the amount of catalyst used, or reduce the temperature of reaction by adding arsmall amount, of initially lower boiling solvent such as benzene, or. use benzene entirely.

Also we have found itdesirableat times-'to useslightly less than apparently the theoretical. amountofdiepoxide, for instance 90% to 95% instead of 100%. "The reason for this mact may reside in the possibility that thei rno V lecular; weight-dimensions on either theresin molecule or the diepoxide .molecule may actually'vary from the true molecular weight by several percent.

PART 6 In preparing oxyalkylated :derivatives of products of' the kind which appear as examples in Part 3, we have found it particularly advantageous to use laboratory oxyethylation. The oxyethylation step is, ofcourse, the

same as the oxypropylation step insofar that two low- The oxyalkylation-susceptible compoundemployed is the one previously described and designated as D1. D1 in turn was obtained from the phenol-formaldehyde resin previously designated as C38 and having a molecular weight of approximately 700. The diepoxide employed was the one previously identified as 3A. See Table I! for more data concerning Example 131.1 17.48 poundsof this resin were dissolved in 18.15 pounds of solvent (xylene) along with 1.75 pounds of finely powdered caustic soda which was employed as a catalyst. Adjustment was made in the autoclaveto operate at a tempera ture of approximately 125 C. to 130 C. and at a pressure of about 10 to 15 poundsper square inch.

The time regulator was set so as to inject the ethylene oxide in approximately one-half hour. he reaction went readily and, as a matter of fact, was completed in less than a half-hour. Stirring was continued fora total time of about minutes. The speed of reaction,:particularly at the low pressure, undoubtedly was due -in a large measure to excellent agitation and also to the high concentration of catalyst; The amount of ethylene oxide equipment which permits continuous.oxypropylationand of diepoxide resin -derivative." The 'theoretical'molecular weight alt-the end .of the-reaction. was approximately 3,5 00.

A comparatively small sampleless than '50 grams, was. withdrawn merely forexamination as far as solubility or emulsifying power. was c,oncerned, and also for the pur-.

x mp e 2 This example simply illustrates the further oxyalkylation ofExample E1 preceding As previously stated the I oxyalkylation-susceptible compound, to wit, D1, present atthe beginning of the stagewas obviously the same as at the end ofthe priorstage (Example E1) to wit, 17.48 pounds. The amount of oxide present in the initial step was 17.5 pounds, the amount of catalyst remained the same, that is, 1.75 pounds, and the amount of solvent remained the same. -The amount of oxide added was another 17.5 pounds, alladditions of oxide in these various stages being based onthe addition of this particular amount. Thus, at the end of the oxyethylation step the amount otoxide added was a total of 35.0pounds and the molal ratio of ethylene oxide to diepoxide resin derivative was approximately to l. The theoretical molecular weight was about 5,250. Conditions as faras temperature and pressure were concerned were the same as in the preceding period. Thisalso applied to the reaction time.

Example E3 3 The oxyalkylation proceeded in the same manner as described in Examples E1 and E2. There was no added solvent and no added catalyst. The oxide added was 17.50 pounds and the total oxide in at'the end of the reaction was 52.5 pounds, The molal ratio of oxide to diepoxideresin derivative was approximately to 1. The temperature and pressure employed were the same as in the two preceding examples but the time of reaction was slightly longer, to wit, one hour.

Example E4 Example E5 The oxyaikylation was continued with the introduction of another 17.5'pounds of ethylene oxide. No added solvent was introduced-and, likewiseno added catalyst was introduced. The theoretical molecular Weight at the end of the agitation period was about 10,500. The time period, however, was increased, slightly to 1 /2 hours instead oto'ne hour. ture and pressure were concerned remained in the preceding examples.

Example E6 the same as The same procedure was tollowed as in the preceding examples with ,the addition of another-17.5 pounds of' ethylene oxide. The total a'mountof oxide added at this.

The conditions as faras temperadiepoxide resin derivative was approximately 240 to 1.'

The theoretical molecular weightof the resin was about 12,250. The conditions of oxyethylation were the same as in previous examples except that the time period was two hours.

- Example E7 The same procedure was followed as in the previous six examples without the addition of either caustic or solvent. The amount of oxide added at the end of the seventhperiod was the equivalent of 122.5 pounds. The molal ratio of oxide to diepoxide resin derivative was about 280 to 1. The molecular weight was approximately 14,000. The reaction had slowed up a bit more and although temperatures and pressures remained the same as in preceding examples, the time period was 2 /2 hours.

Example E8 This was the final oxyalkylation in this particular series. There was no added solvent and no added catalyst. The total amount of oxide added at the end of this step was 140 pounds. The theoretical molecular weight was 26 Column 11 shows the catalyst at the end of the reae' tion period.

Column 12 shows the amount of solvent at the end of the reaction period.

Column 13 shows the molal ratio of ethylene 'oxide to derivative.

15,750. Conditions as far as temperature, pressure and time are concerned were the same as in Example E7, preceding.

The same procedure as described in the previous examples wasemployed in connection with a number of the other condensates described previously. All these data have been presented in tabular form in a series of four tables, Tables VII, VIII, IX and X.

In substantially every case a -gallon autoclave was employed, although in some instances the initial oxyethylation'was started in a 15-gallon autoclave and then transferred to a 25-gallonautoclave. This is immaterial Column 14 can be ignored for the reason that no propylene oxide was employed.

Referring now to Table X. It is to be noted that the first column refers to Examples E1, E2, E3, etc.

The second column gives the maximum temperature employed during the oxyalkylation step and the third column gives the maximum pressure.

The fourth column gives the time period employed.

The last three columns show solubility tests by shaking a small amount of the compound, including the solvent present,'with several volumes of Water, xylene and kerosene. It sometimes happens that although xylene in comparatively small amounts will dissolve in the concentrated material, when the concentrated material in turn is diluted with xylene separation takes place.

Referring now to Table VIII, Examples E57 through E112 are the counterparts of Examples E1 through E56, except that the oxide employed is propylene oxide instead of ethylene oxide. Therefore, as explained previously, 3 columns are blank, to wit, columns 4,9 and 13.

Reference is now made to Table IX. It is to be noted these compounds are designated by F numbers, F1, F2, F3, etc., through and including F32. They are derived, in turn, from compounds in the E series, for example, E51, E55, E107, and E111. These compounds involve the use of both ethylene oxide and propylene oxide.

but happened to be a matter ofconvenience only. The

solvent used in all cases was xylene. The catalyst used was finely powdered caustic soda.

Referring now to Table VII it will be noted that compounds El through E56 were obtained by the use of ethylene oxide, whereas E57 through E112 were obtained a I by the use of propylene oxide alone.

Thus in reference to Table VII it is to be noted as follows:

The example number of each compound is indicated in the first column.

The identity of the oxyalkylation-susceptible comand propylene oxide afterward. 7 pounds obtained from E107 to E111 obviously come from Since compounds E1 through E56 were obtained by the use of ethylene oxide, it is obvious that those obtained from E51 to E55, involve the use of ethylene oxide first,

Inversely, those coma prior series in which propylene oxide was used first.

In the preparation of the series indicated by the letter E, as E49 through E56, E105 through E112, the initial E series such E51, E55, E167, and E111, were duplicated and the oxyalkylation stopped at the point designated instead of being carried further as may have been I the case in the original oxyalkylation step. Then oxyalkylation proceeded by using the second oxide as indicated by the previous explanation, towit, propylene V oxide in F1 through F16, and ethylene oxide in F17 pound, to wit, the diepoxide treated resin, is indicated in the second column.

The amount of such derivative used is shown in the third column.

Assuming that ethylene oxide is employed, as happens to be the case in Example E1 through E56, the amount of oxide present in the oxyalkylation derivative is shown in column 4, although in the initial step since no oxide is present there is a blank.

When ethylene oxide is used exclusively the 5th column is blank.

The 6th column shows the amount of powdered caustic soda used as a catalyst, and the 7th column shows the amount of solvent xylene employed.

through F32 inclusive. 7

It is to be noted that reference to the catalyst in Table IX refers to the total amount of catalyst, i. e., the catalyst present from the first oxyalkylation step plus added The 8th column states the amount of alkylene oxide derivative present in the reaction mass at the end of the period.

As pointed out previously, in this particular series the amount of reaction mass withdrawn for examination was so small that it was ignored and for this reason the resin period.

Column 10 can be ignored insofar that no propylene oxide was employed.

catalyst, if any. The same is true in regard to the solvent. Reference to the solvent refers to the total solvent present, i. e., that from the first oxyalkylation step plus added solvent, if any.

It will be noted also that under the molal ratio the l values of both oxides to the resin condensate are included.

The data given in regard to the operating conditions is substantially the same as before and appears in Table X.

The products resulting from these procedures may contain modest amounts, or have small amounts, of the solvents as indicated by the figures in the tables. If desired the solvent may be removed by distillation, and particularly vacuum distillation. Such distillation also may remove tracesor small amounts of uncombined oxide, if present and volatile under the conditions employed.

Obviously, in theruse of ethylene oxide and propylene oxide in combination one need not first use one oxide and then the other, but one can mix the two oxides and thus obtain what may be termed an indifferent oxyalkylation, i. e., no'attempt to selectively addone and then the' other, or any other'variant Needless to say, one could start with ethylene oxide and then'use propylene oxide, and then go back to ethylene oxide, or, inversely, start with propylene oxide, then 27 use ethylene oxide, and thengo back to propylene oxide, OI, one could use acombination in which butyleneoxide I isused along With either one of the'two oxides just mentioned, or a combination of both of them.

' 28 When products of the kind previously described are intended for subsequent-reaction, such as oxyalkylation, the solvent and catalyst may be permitted to remaimforultimate use. I

The resins-Which'are employed as raw-mater1als vary Oxyalkylatton, particularly exhaustive oxyalkylation, from fairly high melting resins to resins meltmg near tends to do a number of th1ngs such as reduce the color, I the boiling pointer" water, to other products whose meltmake the product less vrscous and may even render a ing points are only moderately above ordinary room thin hqurd, and may reduce the amount of alkalinity temperature; Such res1ns vary incolor from almost present, water-White to products WhlCh are dark amber or reddish In any event whether the solvent is tobe removed, or amber in appearance. In some instances they are tacky the product bleached at either stage, is simply a matter sohds, or. even liquids at ordinary room temperatures. of the intended ultimate use. If employed for the resolu- After treatment with d1epox1des of the kind herein emhem of petroleum emuls1ons there 1s no need to eliminate ployed the resultant product is usually at least as dark, any alkalinity and no need to eliminate color or solvent. perhaps darker, than the initial resin. The solvent can If the product 18 to be employed in the manufacture. of be removed readtly by d1st1llat1on, particularly vacuum varrnsh resms the procedure should be conducted 50 as dishllation. The product obtained after treatment with to hold the color at a mlnlmum, or else the final product the descnbed dlepoxide 1s apt to be somewhat softer and or 1ntermcd1ate product can be further bleached 1n the more hqurd than the. or1g1nal material. In some instances usual manner USlHg earth, bleaching chars, or the like. a tackmess deve1opswh1ch 1s suggestive of cross-linking Ult1mately the solvent could be removed 1n any su1table in om b ure anner.- manner by distillation, mcludmg vacuum d1st1llat1on.

TABLE VII Composition before Composition at end M0181 ratio M0160. Ex. No. wt.

O-S* 0-8" Ethl. Propl. Cata- S01- 0S* Ethl. Propl. Oata- Sol- Ethyl. Propl. based cmpd, cmpdn, .oxide, oxide, lyst, vent, 01117111., oxide, oxide, lyst, vent, oxide oxide on theex.No, lbs. lbs. lbs. lbs lbs. 5. lbs. I lbs. lbs lbs. to'oxyto oxyoretieal alky]. silky]. I value snscept. suscept. cmpd. cmpd.

17.48 1.75 18.15= 17.48 17.50 1.75 I 18. 15 I 89.8 8.498 17. 48 1. 75 18. 15 17. 48 35. 0 1. 75 18. 15 79. 5 5. 248 17. 48 .175 18. 15 17.48 52.5 1. 75 18. 15 119.2 6,998 I 17.48 1.75 18.15 17. 48 70.0 1.75 18. 15 159.0 8,748 17.48 1.75 18.15 17.48 87.5 1.75 18. 15 199.0 10,498 17. 48 1. 75 18. 15 I 17. 48 1.05. 0 1. 75 18. 15 238. 2 12. 248 17. 48 1. 75 18.1: 17.48 122. 5 1. 75 18. 15 278. 5 18.998 17. 48 1. 75 18. 15 17. 48 140. 0 1. 75 18. 15 818. 0 15, 748 14. 1. 5 14. 40 14. 40 14. 4 1. 5 14. 4 65. 3 5,748 14. 40 1. 5 14. 40 14. 40 28. 8 1. 5 14. 4 180. 6 8,621 14.40 1.5 14.40 14.40 48.2 1.5 14.4 195.9 11,494 14.40 1.5 14.40 14.40 57.6 1.5 14.4 261.2 14.867 1440 1.5 14.40 14.40 72.0 1.5 14.4 825.5 17,240 14. 40 I 1.5 14.40 14. 40 86.4 1.5 14.4 591.8 20,118 14. 40 1. 5 14. 40 14.140 100. 8 1. 5 14. 4' 462. 0 22, 986 14. 40 1. 5 7 14. 40 14. 40 115. 2 1. 5 14. 4 527. 5 25, 859 16.25 1.5 16.25 16.25 V 16.25 1.5 16.25 78.8 6,508 16.25 1. 5' 16.25- 16.25. 32.50 1.5. 16.25 147.5 9,758 16. 25 82.50 1.5 16. 25 16.25, 48.175 1.5 16. 25 221.5 18,008 16. 25 48. 75 1. 5 16. 25 16.25 65.0 5 1.5 16. 25 295.2 16.258 16. 25 65.0 1.5 16. 25 16.25 81. 25 1.5 16. 25 869.0 19,508 16. 25 81.25 1.5 16. 25 15.25 97. ,1.5 16.25 442.8 22,758 16.25 97.5 1.5 16. 25 16.25 118.75 1.5 16.25 516.5 25,908 16. 25 118. 75 1.5 16. 25 16. 25 130.0 1.5 16. 25 590.5 29,158 19. 56 2.0 19. 56 19. 5 19.50 ,2.0 19.5 44.4 8, 03 19. 56 19. 50 2. 0 19. 56 19. I 89. 0 2. 0 19.56 88. 8 5, 856 19. 55 89. 0 2. 0 19. 56 19. 56 585 I 2. 0 19. 56 133. 2 7, 806 19. 56 58.5 2.0 19. 56 19.56 178.0 2.0, 19.56 177.6 9,756 19. 56 78. 0 2. 0 19. 56 19. 56 97. 5 2. 0 19. 56 222. 0 11, 706 19. 56 97.5 2.0 .19. 56 19. 56 117.01 2.0 I 19.56 266.4 18,656 19. 56 117.0 2.0 19. 56 19.56 136.5 2.0 19.56, 810.8 25,606. 19.55 186. 5 :2. 0 19. 56' 19. 56 156. 0 2. 0 I 27, 556 I 15.40 1.50 15.40 15.40 I 15:5 1.5- 1 6,168 15.40 15.5 1.50 15.40 15.40 81.0 1.5 9,248, 15. 40 '31. 0 1. 50 15. 40 15. 40 46. 5 1. 5 12, 828 15.40 46.5 1.50 14.50 15.40 62.0, 1.5 I I 15,408 15.40 62.0 1.50 15.40 15.40 77.5 1.5 a 18,483, 15. 40 77. 5 1. 50 15. 40 15. 40 98. 0 1. 5 21, 568 15. 40 93.0 1. 50 15. 40 15. 40 108. 5 1. 5, 24, 648 15.40 108.5 1. 50 15. 40 15. 40 124.0 1.5 I 27,728 17.5 1.75 '17.5 17.5 1 17:5 1. 7.5 6,921 17.5 17.5 1.75 17.5 17.,5 850 1. .381: 17.5 85.0 1.75 17.5 17.5 52.5 1. 75 I 13,841 17.5 52.5 1.75 17.5 17.5 70.0 1. 75 17,301, 17.5 70.0 1.75 17.5 17.5, 87.5. 1.75. 20,761

17.5 87.5 1.75 17.5 17.5 105.0 1.75 4 I I 24,221 17.5 105.0 1.75 I 17.5 175112215. 1.75.; 17.5 27,681.; .17.5 122.5 1.75 17.5 17.5- I 1400 5 1.75 17 1680.4 81,141 17.48 1.0 18.15 -17:48 8.75 1.0;; 18.1 19.9 2,628 17. 48 8.75 1.0 18. 15 .1748 17.50 1.0 18.1 89.8 3,498., 17.48 17.50 1.0 18.15 17.48 26.25 1.0 18. 15 I 59.7 4,875 I 17.48 26.25 1.0 18.15 17.48 85.00 1.0 18. 15 79.5 5,248 17.48 85.0 1.0 18.15 17.48 48.75 1.0 18.15 99.5 6,128 17.48 48.75 1.0, 18. 15 17. 48 y: 52. 50- 1.0 18.15- 119. 5. 6,998 17. 48 52.50 1.0 18.15 17.48 61.25, 1.0 18.15 139.3 7, 878- D1 17.48- 61.25 1.0 18.15 17. 48 70.00 1.0: 18.15. 159.0 748 I "Oxyalkylation-susceptible.

33 "TABLE X-Oontinued gard to F1,

. o e h t. 6 v e 9 m m m. m M m m e m a. me m mo mmmdmmmm mmmmmmmww me o od o mdmmmmo mmmododo. Du A m p D wDDDD nnnnn nl emmn Down mDDDDmDmm mm .l S S. l s S S o 1 :1 1s .1 .m D... m m m Pw m m D mm Pm I I I I I I I I I w m I I I m I I I m m .I I I I I m m m m b V. 0 0 00 0 0 0 m 0 n 0 m 0 m X d fld fl fl fl d dd d m d S 0. s v I .m m I m m r. b e e .a a m m Imm m u 0 000 w M m h 3% m m I .1. IIm m I II I II 4 2 1WW WW M22 1 1 mm o T ms PP Mm. v t xm EN in re h oxyalkylatioig NOTE.-In the above table, the time period F9, F17, and F25 is the total time for hot stages. In respect to all others the time period indicated Big flan-1e required to introduce the second alkylene oxide em- D Y PART 7 Conventional demulsifying agents employed in the treatment of oil field emulsions are used as such, or after 7 hexyl alcohol, octyl alcohol, etc., may be employed as diluents. Miscellaneous solvents such as pine oil, carbon tetrachloride, sulfur dioxide extract obtained in the refining of petroleum, etc., may be employed as diluents. Similarly, the material or materials employed as the demulsifying agent of our process may be admixed with one or more of the solvents customarily used in connection with conventional demulsifying agents. l /loreover, said material or materials may be used alone or in admixture with other suitable well-known classes of demuls1fy-- ing agents.

It is well known that conventional demulsifymg agents may be used in ,a water-soluble form, or in an oil-soluble form, or in a form exhibiting both oiland water-solubility. Sometimes they may be used in a form which exhibits relatively limited oil-solubility. However, since such reagents are frequently used in a ratio of 1 to 10,000 or 1 to 20,000, or 1 to 30,000, or even 1 to 40,000, or 1 to 50,000 as in desalting practice, such an apparent insolubility in oil and water is not significant because said reagents undoubtedly have solubility within such concentrations. This same fact is true in regardto the material or materials of our invention when employed as demulsifying agents.

The materials of our invention, when employed as treating or demulsifying agents, are used in the conventional way, well known to the art, described, for example, in Patent 2,626,929, dated January 27, 1953, Part 3, and reference is made thereto for a description of conventional procedures of demulsifying, including batch,-continuous, and down-the-hole demulsification, the process essentially involving introducing a small amount of de-. mulsifier into a large amount of emulsion with adequate admixture with or without the application of heat, and allowing the mixture to stratify.

In many instances the oxyalkylated products herein specified as demulsifiers can be conveniently used Without dilution. However, as previously noted, they may be diluted as desired with any suitable solvent. For instance, by mixing 75 parts by weight of an oxyalkylated derivative, for example, the product of Example F12 with 15 parts by weight of xylene and 10 parts by weight of iso- .propyl alcohol, an excellent demulsifier is obtained. Selection of the solvent will vary, depending upon the solubility characteristics of the oXyalkylated product, and of course will be dictated in part by economic considerations, i. e., cost.

As noted above, the products herein describedmay be used not only in diluted form, but also may be used admixed with some other chemical dernulsifier. A mixture which illustrates such combination is the following:

Oxyalkylated derivative, for example, the product of Example P12,

A cyclohexylamine salt of a polypropylated napthalene monosulfonic acid, 24%;

An ammonium salt of a polypropylated napthalene monosulfonic acid, 24%;

A sodium salt of oil-soluble mahogany petroleum sulfonic acid, 12%;

A high-boiling aromatic petroleum solvent, 15%;

Isopropyl alcohol, 5%.

The above proportions are all weight percents.

PART 8 The intermediate resinous products described in Part 5, preceding, can be oxyalkylated and employed :tor

various purposes and particularly for the resolution of petroleum emulsions of the Water-in-oil type as described in detail in Part 7, immediately preceding.

Such resinous products, however, without being sub- 5 jected to oxyalkylation can serve for other uses as, de-

scribed in U. S. Patent No. 2,610,955, dated September -16, 1952,-to-De Groote and Keiser. Furthermore, such Ifi'esinous materials can be reacted with alkylene imines, such as ethylene imine or propylene imine, to produce 0 cation-activematerials. Instead of an imine, one. may employ what is a somewhat equivalent material, to wit, a ,,dialkylamino-epoxypropane of the structure wherein R and R are alkyl groups. a

It isv not necessary to point out that after reaction with a reactant of the kind described which introduces 25 a basic nitrogen atom the resultant product can then be subjected to the oxyalkylation procedures describedin -detail in Part 6, preceding.

f Referring now to the use of the oxyalkylated products obtained in the manner described in Part 6, preceding, it is to be noted that in addition to their use in the resolution of petroleum emulsions they may be used as emulsifying agents for oils, fats, and waxes, as ingredients in insecticide compositions, or as detergents and Wetting agents in the laundering, scouring, dyeing, tanning and mordanting industries. Theymay also be used for preparing boring for metal-cutting oils and cattle dips, as metal pickling inhibitors, and for pharmaceutical purposes. 7 Not only do, these oxyalkylated derivatives have their -utility assuchbut they can serve as'initial materials for -10 more complicated reactions of the kind ordinarily requiring a hydroxyl radical. Thisincludes esterification, fie'therization, etc. i Q f The oxyalkylated derivatives may be used as valuable .f.fadditivles to lubricating oils, both those derived from 49 petroleum and synthetic lubricating oils. Also, they can .'.be .used as additives to hydraulic brake fluids of the aqueous and nonaqueous' types They may be used in .connection with other processes where they are injected :ll'ltC) an'oil' or'gas well for purpose of removing a mind 50 sheath, increasing the ultimate flow of fluid from the V surrounding strata, and particularly in secondary recovery operations using aqueous flood waters. These f derivatives *also are suitable for use in dry cleaners soaps. H 7 Comparablejcompounds which can serve the various '-purposes previously enumerated, in both the resinous "stage and the oxyalkylated stage, are obtained from another class of resins, i. e., those in which the phenolic "nuclei are separated by a radical having at least a 3- carbonatom chain and are obtained, not by the use of a If single aldehyde but by the use of formaldehyde, in combination witha carbonyl compound selected from the [class of aldehydes and ketones in which there is an alpha -hydrogen atomavailable as in the case of acetaldehyde Qorfaceto'ne. Such jresins almost invariably'involve the use of'a basic catalyst. Such bridge radicals between Q. phenolic nuclei have either hydroxyl radicals or carbonyl radicals, or both, and are invariably oxyalkylation-susilllcieptibl'e and may also enter into more complicated re- --actantswithbasic secondary amines. The bridge radical in the initial'resin has distinct hydrophile character. Such resins or compounds which can be converted readily into such'resins "are describedin the-following patents. P Such analogous,compounds are not includedas part of the instant-invention. e

-Schrimpe; 2,538,884, dated January 23,

U. S. Patent Nos.: 2,191,802, dated February 27, 1940, to Novotny et al.; 2,448,664, dated September 27 1948, to Fife et -al.; 2,538,883, dated January 23, 1951, to 1951, to Schrimpe; 2,545,559, dated March 20, 1951, to Schrimpe; 2,570,389, dated October 9,. 1951, to Shcrimpe.

Having thus described our invention, what we claim as new and desire to obtain by Letters Patent, is:

1. Theprocess of condensing (A) an oxyalkylationsusceptible, fusible, organic solvent-soluble, water-insoluble phenol-aldehyde resin; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is a hydrocarbon radical having at least 4 and not more than 18 carbon atoms and substituted in the 2,4,6 position; and (B) phenolic epoxides containing at least two 1,2-epoxy rings being principally phenolic diepoxides; said epoxides being free from reactive functional groups other than 1,2epoxy and hydroxyl groups, and including additionally cogenerically associated compounds formed in the preparation of said diepoxides; said epoxides being monomers and low molal polymers not exceeding the tetramer; said epoxides being selected from the class consisting of (a) compounds where the phenolic nuclei are directly joined without an intervening bridge radical, and (b) compounds containing a radical in which two phenolic nuclei are joined by a divalent radical selected from the class consisting of ketone residues formed by the elimination of the ketonic oxygen atom, and aldehyde residues obtained by the elimination of the aldehydic oxygen atom, the divalent radical H H g H H the divalent 38 soluble phenol-aldehyde resin; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is a hydrocarbon radical having at least 4 and not more than 18 carbon atoms and substituted in the 2,4,6 position; and (B) a phenolic diepoxide conresidues obtained by the elimination of the aldehydic radical, the divalent sulfone radical, and the divalent monosulfide radical -S, the divalent radical CH SCH and the divalent disulfide radical -S-S-; said phenolic portion of the diepoxide being obtained from a phenol of the structure in which R, and R, and R represent a member of the class consisting of hydrogen and hydrocarbon substituents of the aromatic nucleus, said substituent member having not over 18 carbon atoms; with the proviso that the molar ratio of reactant (A) to reactant-(B) be approximately 2 to 1 respectively; with the further proviso that said reactive compounds (A) and (B) be members of the class consisting of non-thermosetting organic solvent-soluble liquids and low-melting solids; with the final proviso that the reaction product be a member of the class of oxyalkylationand acylation susceptible solvent-soluble liquids and low-melting solids; and said reaction between (A) and (B) being conducted below the pyrolytic point of the reactants and the resultants of reaction.

2. The process of condensing (A) an oxyalkylationsusceptible, fusible, organic solvent-soluble, water-inoxygen atom, the divalent radical the divalent radical, the divalent sulfone radical, and the divalent monosulfide radical S--, the divalent radical and the divalent disulfide radical -S-S-; said phenolic portion of the diepoxide being obtained from a phenol of the structure i II! II in which R, R", and R represent a member of the class consisting of hydrogen and hydrocarbon substituents of the aromatic nucleus, said substitutent member having not over 18 carbon atoms; with the proviso that the molar ratio of reactant (A) to reactant (B) be approximately 2 to 1 respectively; with the further proviso that said reactive compounds (A) and (B) be members of the class consisting of non-thermosetting organic solventsoluble liquids and low-melting solids; with the final proviso that the reaction product be a member of the class of oxyalkyl'ationand acylationasusceptible solvent-soluble liquids and low-melting solids; and said reaction between (A) and (B) being conducted below the pyrolytic point of the reactants and the resu'ltants of reaction.

3. The process of condensing (A) an oxyalkylationsusceptible, fusible, organic solvent-soluble, water-insoluble phenol-aldehyde resin; said resin being derived by reaction between a difun-ction'al monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula 39 it; WhiehiR is a hydrocarbon radicalhaving at least 4 and not more than 18 carbon atoms and substituted in the 2,4,6 position; and (B) a member of the class consisting of (1) compounds of the following formula II o-o- O H: H H: a I Hz in which R represents a divalent radical selected from the class consisting of ketone residues formed by the elimination of the ketonic oxygen atom and aldehyde residues obtained by the elimination of the aldehydric' oxygen atom, the divalent radical the divalent radical, the sulione radical, and the divalent monosulfide radical S,, the divalent radical CH SCH and the divalent disulfide radical SS; and R 0 is the divalent radical obtained by the elimination of a hydroxyl hydrogen atom and a nuclear hydrogen atom from the phenol RI! r in which R, and R", and R represent a member of the class consisting of hydrogen and hydrocarbon substitnents of the aromatic nucleus, said substitutent member having not over 18 carbon atoms; n represents an integer selected from the class of zero and l, and n represents a whole number not greater than 3; and (2) cogenerically associated compounds formed in the prepara tion of (l) preceding, including monoepoxides; with the proviso that the molar ratio of reactant (A) to reactant (B) be approximately 2 to 1 respectively; with the further proviso that said reactive compounds (A) and (B) be members of the class consisting of non-thermosetting organic solvent-soluble liquids and low melting solids; with the final proviso that the reaction product be a member of the class of oxyalltylationand acylation-susceptible solvent-soluble liquids and low-melting solids; and said reaction between (A) and (B) being conducted below the pyrolytic point of the reactants and the resultants F of reaction.

4. The process of condensing (A) an oxyalkylationsusceptible, fusible, organic solvent-soluble, water-insoluble phenol-aldehyde resin; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R" is a hydrocarbon radical having at least 4 and not more than 18 carbon atoms and substituted in the 2,4,6 position; and (B) a member of the class consisting of 1) compounds or" the following formula:

wherein R is essentially analiphatic hydrocarbon bridge, each n. independently has one or the values 0 to 1, and

R is an alkyl radical containing from 1 to 4 carbon atoms, or even 12 carbon atoms, and (2) cogenerically associated compounds formed in the preparation of (1) (B) consist'principally of the monomer as distinguished from other cogeners; the ratio of reactant (A) to reactant (B) being approximately 2 to 1 respectively; with the further proviso that said reactive compounds (A) to (B) be members of the class consisting of non-thermosetting organic solvent-soluble liquids and low-melting solids; with the final proviso that the reaction product be a member of the class of oxyalkylationand acylationsusceptible solvent-soluble liquids and low-melting solids; and said reaction between (A) and (B) being conducted below the pyrolytic point of the reactants and the resultants of reaction.

5. The process of condensing (A) an oxyalkylationsusceptible, fusible, organic solvent-soluble, water-insoluble phenol-aldehyde resin; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R 'is a hydrocarbon radical having at least 4 and not more than 18 carbon atoms and substituted in the 2,4,6 position; and (B) a member of the class consisting of (1) compounds of the following formula and (2) cogenerically associated compounds formed in the preparation of (1) preceding, including monoepoxides, with the proviso that (B) consist principally of the monomer as distinguished from other cogeners; the

ratio of reactant (A) to reactant (B) being in the proportion of approximately two moles of (A) to one mole of (B); with the further proviso that said reactive compounds (A) and (B) be members of the class consisting of non-thermosetting organic solventesoluble liquids and low-melting solids; with the final proviso that the reaction product be a member of the class of oxyalkylationand acylation-susceptible solvent-soluble liquids and low-melting solids; and said reaction between (A) and (B) being conductedbelow the pyrolytic point of the reactants and the resultants of reaction.

6. The product obtained in the process defined in claim 1.

7. The product obtained in the process defined in claim 5.

8. The process of oxyalkylating by means of a compound selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide the reaction products obtained by the process of claim 1. I

9. The process of oxyalltylating by means of a compound selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide the reaction products obtained by the process of claim 2. g

' 10. The process of oxyalliylating by means of a compound selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methyl- 

1. THE PROCESS OF CONDENSING (A) AN OXYALKYLATIONSUSCEPTIBLE, FUSIBLE, ORGANIC SOLVENT-SOLUBLE, WATER-INSOLUBLE PHENOL-ALDEHYDE RESIN; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF TRIFUNCTIONAL PHENOLS; SAID PHENOL BEING OF THE FORMULA 